Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2420/00—Metallocene catalysts
  • C08F2420/11—Non-aromatic cycle-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by a non-aromatic cycle

Definitions

• the present invention relates to a process for the preparation of cycloolefin copolymers.
• cycloolefin homopolymers and copolymers can be prepared using metallocene-aluminoxane catalyst systems (EP 283 164, EP 407 870).
• the polymerization of the cycloolefins proceeds with retention of the cycles and can be carried out in solvents or in bulk.
• Cycloolefin copolymers can be made with a high cycloolefin content and then have a high glass transition temperature. This is associated with a high thermal dimensional stability, which is why these polymers are suitable for use as thermoplastic molding compositions.
• Cycloolefin copolymers Two sets of properties can be distinguished in cycloolefin copolymers which are produced using metallocene technology. Cycloolefin copolymers that are made with mirror-symmetric metallocenes have relatively low tensile stresses. Cycloolefin copolymers, which are produced by using C 2 -symmetrical or unsymmetrical metallocenes, are distinguished in comparison by high tensile stresses. Metallocenes, which are suitable for the production of cycloolefin copolymers with high tensile stress at break, provide relatively low mass averages of the molecular weight and have an unsatisfactory polymerization activity (P 4304307.0).
• the invention thus relates to a process for the preparation of a cycloolefin copolymer by polymerizing at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst which contains at least one cocatalyst and at least one stereorigid metallocene compound, the stereorigid metallocene compound as ligand having at least two substituted or unsubstituted cyclopentadienyl groups which are connected to one another via a five-membered ring, at least one cyclopentadienyl group being fused to the connecting five-membered ring.
• a cyclopentadienyl group as a substituent on the connecting five-membered ring (ie the cyclopentadienyl group is via a covalent bond to the connecting five-membered ring), while another cyclopentadienyl group is fused to the connecting five-membered ring.
• the cyclopentadienyl groups can be unsubstituted or substituted.
• the cyclopentadienyl group fused to the connecting five-membered ring is preferably unsubstituted.
• Substituted cyclopentadienyl groups preferably carry one or more C 1 -C 30 carbon-containing radicals such as C 1 -C 10 alkyl, C 6 -C 20 aryl (for example phenyl or naphthyl) or two or more of the C 1 -C 30 carbon-containing radicals form a ring system.
• C 1 -C 30 carbon-containing radicals such as C 1 -C 10 alkyl, C 6 -C 20 aryl (for example phenyl or naphthyl) or two or more of the C 1 -C 30 carbon-containing radicals form a ring system.
• substituted cyclopentadienyl groups are methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadylyl, methyl, ethylenedilyl, ethylenylindenyl, ethylenedilyl, indenyl, methyl, Methyl-naphthyl-indenyl, methyl-iso-propyl-indenyl, benzoindenyl, methyl-4,5-benzoindenyl, methyl- ⁇ -acenaphthindenyl, methyl-di-iso-propylindenyl, fluorenyl, methylfluor
• the connecting five-membered ring of the metallocene compound used in the process according to the invention is preferably an aliphatic and can also contain heteroatoms such as nitrogen, oxygen, sulfur, silicon or germanium.
• the connecting five-membered ring can also carry substituents such as C 1 -C 40 carbon-containing groups (for example C 1 -C 10 alkyl or C 6 -C 20 aryl).
• the central unit M 1 R x n of the metallocene compound used in the process according to the invention preferably consists of a transition metal atom M 1 , in particular of group IIIb, IVb, Vb or VIb of the periodic table of the elements, which carries n substituents R x , which are the same or different and preferably a C 1 -C 40 carbon-containing group, a halogen atom, a OH group or a hydrogen atom.
• the sum of the number of substituents R x and the number of substituted or unsubstituted cyclopentadienyl groups (ligands) corresponds to the valence of the transition metal atom M 1 .
• a stereorigid metallocene compound of the formula I is preferably used in the process according to the invention wherein M 1 is a metal from group IIIb, IVb, Vb or VIb of the periodic table, M 2 is carbon, silicon or germanium, R 1 and R 2 are the same or different and are a hydrogen atom, a C 1 -C 40 carbon-containing group such as a C 1 -C 10 alkyl, a C 1 -C 10 alkoxy, a C 6 -C 10 aryl -, a C 6 -C 25 aryloxy, a C 2 -C 10 alkenyl, a C 7 -C 40 arylalkyl or a C 7 -C 40 arylalkenyl group, an OH group, a halogen atom or NR 15 2 , in which R 15, identical or different, are a halogen atom, a C 1 -C 10 alkyl group or a C 6 -C 10 aryl group or form a
• M 1 is a metal from group IVb of the periodic table of the elements such as titanium, zirconium or hafnium, in particular zirconium
• R 1 and R 2 are the same and represent a C 1 -C 4 alkyl group or a halogen atom such as fluorine, chlorine, bromine or iodine, in particular chlorine
• R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are the same or different and are a hydrogen atom, a C 1 -C 10 alkyl group or a C 6 -C 24 aryl group, or two or more adjacent radicals R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 together with the atoms connecting them form an aromatic or aliphatic carbon-containing ring system with 4 to 20 carbon atoms
• R 10 is a hydrogen atom, a C 6 -C 24 aryl group or a C 1 -C 10
• R 1 and R 2 are the same and represent a halogen atom, in particular chlorine
• R 3 , R 4 , R 5 , R 6 , R 7 and R 9 are identical or different and are a hydrogen atom or a C 1 -C 4 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl or a C 6 - C 14 aryl group such as phenyl or naphthyl, or R 3 and R 4 and / or R 5 and R 6 together with the atoms connecting them form an aromatic hydrocarbon ring system with 4 to 20 carbon atoms, in particular a six-membered ring, which in turn can be substituted
• R 8 is a hydrogen atom
• M 2 is a carbon atom
• R 10 is a hydrogen atom, a C 1 -C 6 alkyl group, in particular methyl, or is a C 6
• a stereorigid metallocene compound is used in the process according to the invention, which has a ligand system which consists of 4- [ ⁇ 5 -3'-alkyl-cyclopentadienyl) -4,6,6-trimethyl- ( ⁇ 5 -2-alkyl-4, 5-tetrahydropentalene]
• a ligand system which consists of 4- [ ⁇ 5 -3'-alkyl-cyclopentadienyl) -4,6,6-trimethyl- ( ⁇ 5 -2-alkyl-4, 5-tetrahydropentalene]
• R 3 , R 5 , R 6 , R 7 and R 9 is different from hydrogen and / or R 8 is hydrogen.
• metallocene compounds used in the process according to the invention are: [4- ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -4,5-tetrahydropentalen)] - dichlorotitanium [4- ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -4,5-tetrahydropentalen)] - dichlorozirconium [4- ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -4,5-tetrahydropentalen)] - dichlorohafnium [4- ( ⁇ 5 -cyclopentadienyl) -4-methyl- ( ⁇ 5 -4,5-tetrahydropentalen)] - dichlorozirconium [4- ( ⁇ 5 -cyclopentadienyl) -4-ethyl- ( ⁇ 5 -4,5-tetrahydropentalen)] - dichlorozirconium [4- ( ⁇ 5 -cyclopentadienyl
• M 4 is a metal from main group Ia, IIa or IIIa of the periodic table of the elements.
• the compounds of formula IIb can be prepared from ⁇ , ⁇ -unsaturated ketones (Chem. Ber. 123, 549 (1990), J. Org. Chem. 54, 4981 (1989)) by methods known from the literature.
• reaction of the compound of formula IIb to ligand system III takes place by reaction with an organometallic compound (such as, for example, cyclopentadienyllithium, indenyllithium, fluorenyllithium) or Grignard reagents.
• organometallic compound such as, for example, cyclopentadienyllithium, indenyllithium, fluorenyllithium
• Grignard reagents such as, for example, cyclopentadienyllithium, indenyllithium, fluorenyllithium
• the salts of the formula III can be converted directly to the corresponding dianion compounds of the formula V by deprotonation with, for example, butyllithium.
• the hydrolysis of compound III leads to Formation of the biscyclopentadiene compound IV, which is obtained as a mixture of constitutional isomers and can be purified by chromatography.
• the dianion compound of the formula V is formed by double deprotonation of IV with, for example, butyllithium.
• Metallocenes of the formula VI can be reacted with organometallic compounds such as Grignard reagents or hydrocarbon-lithium reagents to give metallocenes of the formula I in which R 1 and R 2 are not halogen.
• organometallic compounds such as Grignard reagents or hydrocarbon-lithium reagents
• the reaction to the bridged metallocenes of the formula VI and the isolation of the desired complexes is known in principle.
• the dianion of formula V is reacted in an inert solvent with the corresponding metal halide, such as zirconium tetrachloride.
• the metallocenes of the formula VI can also be synthesized directly from the difulvenes of the formula II without isolation of the intermediates.
• Suitable solvents are aliphatic or aromatic solvents such as hexane or toluene, ethereal solvents such as tetrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene.
• a further possibility for the preparation of the metallocene compounds according to the invention consists in the reaction of the ligand precursor VII with the cyclopentadiene VIII, both of which can be prepared in accordance with the regulations known from the literature.
• the compounds IX can be thermally cyclized to the ligand precursors X according to a procedure known in the literature (Chem. Ber. 120, 1611 (1987)).
• X is converted to XI using an organometallic compound (such as cyclopentadienyllithium, indenyllithium, fluorenyllithium) or Grignard reagents.
• the dianion compound of formula Va can be obtained directly by reacting X with an organometallic reagent (such as phenyllithium, methyl lithium, n-butyllithium or Grignard reagents).
• organometallic reagent such as phenyllithium, methyl lithium, n-butyllithium or Grignard reagents.
• the hydrolysis of Va with water leads to the generation of ligand precursors IV.
• the reaction to the bridged metallocenes of the formula VIa and the isolation of the desired complexes is known in principle.
• the dianion of formula Va is in an inert solvent with the corresponding metal halide such as Zirconium tetrachloride implemented.
• the metallocenes of the formula VIa can also be synthesized directly from the fulvenes of structure X without isolation of the intermediates.
• Suitable solvents are aliphatic or aromatic solvents such as hexane or toluene, ethereal solvents such as tetrahydrofuran or diethyl ether or halogenated hydrocarbons, such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene.
• the biscyclopentadienyl compounds of the formula IV in which at least one of the radicals R 3 to R 6 and at least one of the radicals R 7 to R 9 is hydrogen and at least one of the radicals R 3 to R 9 is different from hydrogen can be known from the literature Methods for the fulvenes of the formula IVb or IVc are implemented. This is to be illustrated by the following reaction scheme, where R 16 , R 17 , R 19 and R 20 are the same or different and are defined as R 10 .
• organometallic compounds of the formula R 18 M 5 (where R 16 , R 17 , R 18 , R 19 and R 20 are the same or different and are defined as R 10 ; M 5 is defined as M 4 ) to form the monoanion compound III.
• R 18 M 5 is defined as M 4
• the compounds of the formula XII in which at least one of the radicals R 3 to R 6 and at least one of the radicals R 7 to R 9 is hydrogen, can be converted to the metallocenes according to the invention.
• R 12 in the compounds of the formulas IIb, III, IV, V, VI, X, XI, Va, VIa, IVb, IVc, Vb, Vc and XII is hydrogen.
• R 14 in the compounds of the formulas X, XI, Va and VIa is hydrogen.
• the salts of the formula IIIb can be converted directly to the corresponding dianion compounds of the formula Va by deprotonation with, for example, butyllithium.
• the conversion to the bridged metallocenes of the formula I takes place in accordance with the reaction from V to VI.
• the metallocenes according to the invention are highly active catalyst components for cycloolefin copolymerization. Depending on the substitution pattern of the ligands, the metallocenes can be obtained as a mixture of isomers. The metallocenes are preferably used isomerically pure. The use of the racemate is sufficient in most cases.
• the pure enantiomer in the (+) or (-) form can also be used.
• An optically active polymer can be produced with the pure enantiomers.
• the configuration-isomeric forms of the metallocenes should be separated, since the polymerization-active center (the metal atom) in these compounds produces a polymer with different properties. For certain applications, for example soft molded articles, this can be desirable.
• a metallocene compound and a cocatalyst are preferably used. Mixtures of two or more metallocene compounds can also be used, in particular for the production of reactor blends or of cycloolefin copolymers with a broad or multimodal molar mass distribution.
• an aluminoxane is preferably used as the cocatalyst, which preferably has the formula XIIIa for the linear type and / or the formula XIIIb for the cyclic type, wherein in formulas XIIIa and XIIIb the radicals R 22 are the same or different and a C 1 -C 6 alkyl group, a C 6 -C 18 aryl group, benzyl or hydrogen mean, and p is an integer from 2 to 50, preferably 10 to 35.
• the radicals R 22 are preferably the same and are methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
• radicals R 22 are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in a number of 0.01-40% (of the radicals R 22 ).
• the aluminoxane can be prepared in various ways by known methods.
• One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene).
• an inert solvent such as toluene
• AlR 3 + AlR ' 3 two different aluminum trialkyls (AlR 3 + AlR ' 3 ) are reacted with water according to the desired composition (S. Pasynkiewicz, Polyhedron 9 (1990) 429, EP-A 302 424).
• aluminoxane it is also possible to apply the aluminoxane to a support and then to use it as a suspension in a supported form.
• Several delivery methods are known (EP 92107331.8), e.g. silica gel can act as a carrier.
• metallocene in the polymerization reaction preactivate with a cocatalyst, especially an aluminoxane. This significantly increases the polymerization activity.
• the transition metal compound is preactivated in solution.
• the metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon.
• An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon.
• Toluene is preferably used.
• the concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total solution.
• the metallocene can be used in the same concentration, but preferably it is used in an amount of 10 -4 - 1 mol per mol of aluminoxane.
• the preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. One works at a temperature of -78 ° C to 100 ° C, preferably 0 to 70 ° C.
• a prepolymerization can be carried out using the metallocene.
• the (or one of the) olefin (s) used in the polymerization is preferably used.
• the metallocene can also be applied to a support.
• Suitable carriers are, for example, silica gels, aluminum oxides, solid aluminoxane or other inorganic carrier materials.
• a suitable carrier material is also a polyolefin powder in finely divided form.
• a further possible embodiment of the process according to the invention consists in using a salt-like compound of the formula R x NH 4 -x BR ' 4 or the formula R 3 PHBR' 4 as a cocatalyst instead of or in addition to an aluminoxane.
• X 1, 2 or 3
• R alkyl or aryl, the same or different
• R ' aryl, which can also be fluorinated or partially fluorinated.
• the catalyst consists of the reaction product one Metallocens with one of the compounds mentioned (EP-A 277 004).
• solvent is added to the reaction mixture, then it is common inert solvents such as e.g. aliphatic or cycloaliphatic hydrocarbons, gasoline or hydrogenated diesel oil fractions or toluene.
• the metallocenes are preferably used in the form of their racemates.
• the metallocene compound is preferably used in a concentration, based on the transition metal, of 10 -3 to 10 -8 , preferably 10 -4 to 10 -7 mol, transition metal per dm 3 reactor volume.
• the aluminoxane is used in a concentration of 10 -4 to 10 -1 , preferably 10 -4 to 2 * 10 -2 mol per dm 3 reactor volume, based on the aluminum content. In principle, however, higher concentrations are also possible.
• the polymerization can be carried out in the liquid cycloolefin itself or in cycloolefin solution, the pressure advantageously being above 1 bar.
• the cyclic olefin used in the process according to the invention can be mono- or polycyclic, it is preferably polycyclic.
• the acyclic olefin used in the process according to the invention is preferably a 1-olefin with preferably 2 to 40 C atoms.
• At least one polycyclic olefin preferably of the formulas XIV, XV, XVI, XVII, XVIII or XIX , wherein R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are the same or different and denote a hydrogen atom or a C 1 -C 40 hydrocarbon radical, the same radicals in the different formulas can have different meanings.
• At least one cycloolefin of the formulas XIV or XVI is particularly preferably used, in which R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are identical or different and a hydrogen atom or a C 1 -C 40 hydrocarbon radical, in particular a C 6 -C 20 aryl radical or a C 1 -C 10 alkyl radical mean, where the same radicals in the different formulas can have different meanings.
• the acylic olefin used in the process according to the invention preferably has the formula XX wherein R 31 , R 32 , R 33 and R 34 are the same or different and represent a hydrogen atom or a C 1 -C 20 hydrocarbon radical, preferably a C 6 -C 10 aryl radical and a C 1 -C 10 alkyl radical. Ethylene and propylene are preferred.
• a monocyclic olefin of the formula XXI where n is a number from 2 to 10 is used.
• copolymers of polycyclic olefins preferably of the formulas XIV and XVI, are produced with ethylene.
• Particularly preferred polycyclic olefins are norbornene and tetracyclododecene, which may be substituted by (C 1 -C 6 ) alkyl. They are preferably copolymerized with ethylene; ethylene / norbornene copolymers and ethylene / tetracyclododecene copolymers are of particular importance.
• the cyclic olefin is used in an amount of 0.1 to 99.9% by weight and the acyclic olefin in an amount of 0.1 to 99.9% by weight, based in each case on the total amount of the monomers.
• the concentration of the acyclic olefin used results from its solubility in the reaction medium at a given pressure and temperature.
• Mixtures of two or more olefins of the respective type are also to be understood as cyclic olefins and acyclic olefins.
• Copolymers of monocyclic olefins and acyclic olefins can also be obtained by the process described.
• cyclopentene which may be substituted, is preferred.
• the process according to the invention is preferably carried out at temperatures from -78 to 200 ° C., in particular 0 to 100 ° C., and a pressure of 0.01 to 64 bar.
• the molar ratios of the cyclic olefin to the acyclic olefin used can be varied within a wide range. Molar ratios of 3: 1 to 100: 1 cycloolefin to open-chain olefin are preferably used.
• the choice of the polymerization temperature, the concentration of the catalyst components and the molar ratio used or the pressure of the gaseous, open-chain olefin allow the rate of comonomer incorporation to be controlled almost as desired. Incorporation rates between 20 and 80 mol% of the cyclic components are preferred, and incorporation rates between 40 and 60 mol% of the cyclic components are particularly preferred.
• the polymerization can also be carried out in several stages, and block copolymers can also be formed (P 42 05 416.8).
• the average molecular weight of the polymer formed can be further controlled in a known manner by metering in hydrogen, varying the catalyst concentration or varying the temperature.
• the polydispersity M w / M n of the copolymers is quite narrow with values from 1.9 to 3.5. This results in a property profile that makes them particularly suitable for injection molding.
• the process according to the invention can be used to produce amorphous cycloolefin copolymers which do not contain any semi-crystalline ethylene polymers.
• the copolymers are transparent, hard and thermoplastically processable.
• the tensile stress at break (in accordance with DIN 53457) is preferably in the range from 50 to 100 MPa, in particular between 55 and 70 MPa. No decomposition reactions or a reduction in viscosity were found at temperatures of 300 ° C either during extrusion or injection molding.
• the materials produced according to the invention are particularly suitable for the production of moldings such as extrusion parts (for example foils, tubes, tubes, rods and fibers) or injection molded articles of any shape and size.
• An important property of the materials according to the invention is their transparency.
• the refractive index of the reaction products described in the following examples determined with an Abbe refractometer and mixed light, is in the range between 1.520 and 1.555.
• the products according to the invention can be used as a replacement for glass, for example lenses, prisms, carrier plates and foils for optical data storage, for video disks, for compact disks, as a deck - and Focusing disks for solar cells, as cover and diffusing disks for performance optics, as optical fibers in the form of fibers or foils.
• the materials produced according to the invention can be used as a structural material in various technical fields (P 42 13 219.3).
• the polymers obtained according to the invention can also be used for the production of polymer alloys.
• the alloys can be made in the melt or in solution.
• the alloys each have a combination of properties of the components that is favorable for certain applications.
• the following polymers can preferably be used for alloys with the polymers according to the invention:
• the process according to the invention provides transparent cycloolefin copolymers which have high tear strengths.
• the glass transition temperatures Tg given in the following examples were determined by means of DSC (differential scanning calorimetry) at a heating rate of 20 ° C./min.
• the specified viscosity numbers were determined in accordance with DIN 53728.
• the mechanical properties were measured in the tensile elongation test (DIN 53457, Instron 4302).
• 600 cm 3 of an 85% strength by weight solution of norbornene in toluene are placed in a 1.5 dm 3 autoclave which has been thoroughly rinsed with ethene beforehand.
• the solution was saturated with ethene by pressing ethene (18 bar) several times.
• 5 dm 3 of toluene methylaluminoxane solution (10.1% by weight methylaluminoxane solution with a molecular weight of 1300 g / mol after cryoscopic determination) were metered in countercurrent into the reactor thus prepared and stirred at 70 ° C. for 30 minutes.
• the mixture was polymerized for one hour with stirring (750 rpm), the ethene pressure being kept at 18.0 bar by metering in further quantities.
• the polymerization mixture was drained into a vessel and immediately introduced into 5 dm 3 of acetone, stirred for 10 minutes and then the precipitated product was filtered.
• the filter cake was washed three times alternately with 10% hydrochloric acid and acetone. Finally, it was washed neutral with water, the residue was slurried in acetone and filtered again.
• the polymer purified in this way was dried at 80 ° C. under reduced pressure (0.2 bar) for 15 hours.
• 600 cm 3 of an 85% strength by weight solution of norbornene in toluene are placed in a 1.5 dm 3 autoclave which has been thoroughly rinsed with ethene beforehand.
• the solution was saturated with ethene by pressing ethene (18 bar) several times.
• 5 dm 3 of toluene methylaluminoxane solution (10.1% by weight methylaluminoxane solution with a molecular weight of 1300 g / mol after cryoscopic determination) were metered in countercurrent into the reactor thus prepared and stirred at 70 ° C. for 30 minutes.
• the mixture was polymerized for one hour with stirring (750 rpm), the ethene pressure being kept at 18.0 bar by metering in further quantities.
• the polymerization mixture was drained into a vessel and immediately introduced into 5 dm 3 of acetone, stirred for 10 minutes and then the precipitated product was filtered.
• the filter cake was washed three times alternately with 10% hydrochloric acid and acetone. Finally, it was washed neutral with water, the residue was slurried in acetone and filtered again.
• the polymer purified in this way was dried at 80 ° C. under reduced pressure (0.2 bar) for 15 hours.
• 600 cm 3 of a 70% by weight solution of norbornene in toluene are placed in a 1.5 dm 3 autoclave, which has been thoroughly rinsed with ethene beforehand.
• the solution was saturated with ethene by pressing ethene (16 bar) several times.
• 5 dm 3 of toluene methylaluminoxane solution (10.1% by weight methylaluminoxane solution with a molecular weight of 1300 g / mol after cryoscopic determination) were metered in countercurrent into the reactor thus prepared and stirred at 70 ° C. for 30 minutes.
• the mixture was polymerized for one hour with stirring (750 rpm), the ethene pressure being kept at 16.0 bar by metering in more.
• the polymerization mixture was drained into a vessel and immediately introduced into 5 dm 3 of acetone, stirred for 10 minutes and then the precipitated product was filtered.
• the filter cake was washed three times alternately with 10% hydrochloric acid and acetone. Finally, it was washed neutral with water, the residue was slurried in acetone and filtered again.
• the polymer purified in this way was dried at 80 ° C. under reduced pressure (0.2 bar) for 15 hours.
• Example 2 The procedure was as in Example 1, but isopropylidene (cyclopentadienyl) (1-indenyl) dichlorozirconium was used as the metallocene compound. 89 g of polymer were obtained, which had a glass transition temperature of 150 ° C., a viscosity number of 57 cm 3 / g, a tensile stress at break of 61 MPa and an elongation at break of 3.3%. The activity A * was 34000 g polymer / hx mmol.

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